Trace element determination in rocks and sediments by neutron activation analysis

Neutron activation analysis (NAA) is one of the most used analytical techniques for trace element determination in rocks, because time consuming operations are avoided. We have analyzed different types of USGS reference materials (G-2, GSP-1, BHVO-1, STM-1, GXR-3, GXR-4, GXR-5), using both thermal (TNAA) and epithermal neutrons (ENAA). ENAA has been used to reduce interferences due to Sc-46 and to other high activities. The following elements have shown an improvement when analyzed by ENAA: Ba, Cs, Gd, Rb, Sb, Sr, Ta, Tb, Th, Tm, U, Yb, Zr; better results were found for Ce, Co, Cr, Eu, Fe, Hf, La, Lu, Na, Nd, Sc, Zn with TNAA. The accuracy of both methods has been tested comparing our results with some published values. The agreement is in general very good. The precision also is satisfactory, being for many elements better than 10%. After these tests, a study on some rock samples from the basaltic plateau of Kenya, east of Gregory Rift, has been performed by ENAA. Among the elements determined in this work, the rare earch elements (REE) can give significant petrogenetic information, by means of their distribution and fractionation in the rocks. The main parameters investigated are the degree of fractionation of light (La to Eu) relative to heavy (Gd to Lu) REE and the occurence of Eu anomalies, when the REE concentrations are compared to chondritic values. The evaluation of detection limits by TNAA has been performed for REE in sediment samples from Thyrrenian Sea (Central Italy).     

Trace element determination in high-purity aluminum clad samples by k 0-based internal monostandard instrumental neutron activation analysis

The k₀-based internal monostandard instrumental neutron activation analysis (IM-INAA) method was applied for quantification of trace impurities in seven high purity aluminum samples used as fuel cladding in a research reactor. Samples along with BCS CRM 182 (Si–Al alloy) were irradiated in high flux reactor neutrons for 10–15 h. In situ detection efficiency, needed in concentration calculation ratio by IM-INAA, was obtained using gamma rays of activation products produced in the samples. Elemental concentration ratios obtained with respect to Fe (used as internal monostandard) were converted to absolute concentrations by determining concentration of Fe by relative method of NAA. Concentrations of ten trace elements (Sc, Cr, Co, Zn, Ga, La, Ce, Sm, W and Hf) including major element Fe were determined in this work. The method used is non-destructive in nature and does not need multielement standards. Results of IM-INAA were compared with those obtained by relative method of INAA and inductively coupled plasma atomic emission spectrometry (ICP-AES). Details of methodologies and results obtained by all methods are discussed and compared in the paper.     

Trace element determination in aerosols from the Antarctic Peninsula by neutron activation analysis

The knowledge of the composition of atmospheric aerosols in remote areas, like the Antarctic Peninsula is of great importance for the study of long-range transport of atmospheric contaminants and also from the climatological point of view. Instrumental neutron activation analysis was applied in the present work to determine the elements Al, V, Mn, Na, Cl, Ca, Au, Br, Sb, Sc, Fe, Zn, K, Th and La in aerosol samples collected in the Brazilian Antarctic Station Comandante Ferraz (62° S, 58° W) located on King George Island in the Antarctic Peninsula. The sources of the aerosols were investigated by means of Enrichment Factors and Principal Factor Analysis. Both methods yielded similar results. Sea and soil were identified as the major sources of aerosols, in the samples collected at the Brazilian Station.     

Trace characterization of high-purity nickel by instrumental and radiochemical neutron activation analysis

Summary The high activity of the radionuclides ⁶⁵Ni (t_1/2=2.52 h) and ⁵⁸Co (t_1/2=70.8 d) imposes severe limitations on the performance of direct instrumental neutron activation analysis of nickel. The extent of the interference of the ⁵⁸Co depends on the ratio of the fluxes of the fast and thermal neutrons. A method of selective removal of cobalt, based on extraction with -nitroso--naphthol has been developed for the purpose of radiochemical NAA. Separation yields have been determined for 36 elements. The detection limits obtainable with both the instrumental and the radiochemical method are <10^–4 g/g for the elements Au, Eu, Ir, La, Sc and Sm, between 10^–4 and 10^–3 g/g for Cr, Cs, Hf, Hg, Lu, Re, Sb, Ta, Th, Tm and Yb, between 10^–3 and 10^–2 g/g for As, Ag, Br, Ce, Ga, Na, Ru, Se, W and Zn, and in the range 0.01–1 g/g for Ba, Cd, Co, Fe, In, K, Mo, Nd, Pd, Rb, Sn, U and Zr.     

Determination of tin in indium by neutron activation with pre-irradiation separation

A method has been developed for chemical control of a short-lived radiopharmaceutical,⁵²Fe. The optimum conditions have been investigated for the simultaneous determination of microgram amounts of nickel, iron and chromium in an admixture. The method developed is applicable for the determination of 0.01 to 20 μg·ml^?1 of nickel, 0.01 to 50 μg·ml^?1 of iron and 0.05 to 50 μg·ml^?1 of chromium. A study has been made of the mutual interference of these elements at different concentrations, and also of the interference by various other cations and anions. A list has been given of the other elements that can be analysed using the supporting electrolyte. A method of routine analysis is described.     

Trace element determination in suspended matter and in sedimetns-by instrumental neutron activation analysis

By means of instrumental neutron activation, more than 20 trace elements are determined in suspended matter in Rhine water, Main water and Rhine sediments. Monoelement and multielement standards are used for calibration. Sample collection, separation of suspended matter by filtration or centrifugating and sample preparation are described. The results obtained by filtration and by centrifuging are compared. Interferences in evaluation of the γ-spectra and their influence on the results are discussed. Systematic errors are detected by participation in ring analysis.     

A pre-irradiation separation procedure based on ion-exchange chromatography for gallium determination in biological and environmental materials by neutron activation analysis

A pre-irradiation separation procedure, for gallium determination in biological and environmental materials by neutron activation analysis (NAA) is reported. The proposed method, based on ion-exchange chromatography, allows to eliminate the radiation risk, while taking the advantages of high sensitivity of NAA. The single comparator method is employed for gallium quantitative evaluation. Since no standard reference materials with certified gallium contents were available, the reliability of the proposed method was extensively investigated by various approaches. Four biological and one environmental standard reference materials, with gallium contents ranging from 54 g/g-3 ng/g, have been analyzed.     

The determination of vanadium in geological materials by activation analysis with pre-irradiation separation

Vanadium is determined in silicate rocks by neutron activation after dissolution of the samples with HF/HNO₃ and separation by solvent extraction. The chemical yield of the pre-irradiation separation is determined by means of ⁴⁸V tracer. Results for 15 U.S. Geological Survey standard rocks are presented and discussed in relation to literature data. The method is especially useful at vanadium concentrations below 10 ppm, where purely instrumental neutron activation as well as other techniques commonly used for vanadium determinations in rocks, have inadequate sensitivity.     

Trace element analysis of motor oil by reactor neutron activation analysis

Normal motor oil have been analyzed by RNAA using thermal neutrons and single comparator method. The samples were taken from the oil carter of an engine. The concentration of trace elements have been measured as a function of running kilometers by -ray spectrometry. The trace elements which have been detected are Na, Mg, Al, Cl, V, Mn, Cu, Cr, Fe, Co, Zn, Br, Sb and Cd.     

Trace element analysis of human blood serum by neutron activation analysis

An attempt was made to see if there is any correlation between the trace element concentrations in the human blood serum and some specific disease. The serum samples of the patients suffering from cancer, Down syndrome, and Banti syndrome were analyzed by the neutron activation method and compared with the trace element concentrations observed among the clinically healthy men. The cancer patients gave below normal concentrations in Rb, Mn, Fe, Co, Cu, Zn, Al and Se. The Down syndrome patients were found to have similar deficiencies in Cr, Mn, Fe, Co, Zn, Cu and Sb.     

Trace element analysis of biological materials by thermal and epithermal neutron activation analysis

A scheme for instrumental neutron activation analysis of biological materials is proposed. The scheme is based on a combination of thermal and epithermal activation. The accuracy is evaluated by analyzing 4 standard reference materials. Results from the analysis of human blood serum and plasma are given.     

Trace element pharmacognostical study on diuretic drugs by neutron activation analysis

Some pharmacological properties and especially diuretic action of medicinal plants are attributed to their elemental content. The elements chlorine, manganese, potassium and sodium are determined by instrumental neutron activation analysis in the dry samples of the following drugs: stigmata of Zea mays, leaves of Uva ursi, rhizome of Cynodon dactylon, whole plant of Ceterach officinarum as well as in infusions, decoction of the same drugs and in the water used for these preparations. It has been found that manganese and potassium are transferred partially into prepared solutions. Sodium is not transferred into solutions from any of these drugs while only chlorine is transferred partially into infusion of Zea mays. From these results it is concluded that the diuretic action of the examined drugs should not be attributed exclusively to the presence of their potassium and chlorine content but also to other constituents.     

Trace element analysis of high-purity copper

Summary In copper samples trace impurities of the elements As, Bi, Cr, Fe, Pb, Sb, Se and Te in the low g/g range were coprecipitated with lanthanum hydroxide and determined by flame AAS (Fe) and electrothermal AAS (other elements). Reduction of the sample weight results in a considerable saving of time compared to elder procedures and allows to apply centrifugation instead of filtration as separation technique, by which the risk of contamination is decreased. The completeness of separation was examined by analyzing standard solutions. Additionally radio tracer experiments were employed with Sb and Se. Based on recovery data, a classification scheme was set up with regard to adsorption behaviour. High-purity copper samples were analyzed by the procedure described; INAA and ICP-MS were used as comparison methods. Parameters affecting the precision were examined; the main influence was caused by the separation step. The procedure is well suitable for the determination of 2–10 g/g As, Cr and Pb and 5–50 g/g Fe in high-purity copper.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Trace element exposure in man by instrumental neutron activation analysis of hair

A nondestructive instrumental neutron activation technique was used to analyze human hair samples collected from people living in metropolitan and rural areas in Korea. Samples were also collected from factory workers and cancer patients. Hair from metropolitan area residents contain higher concentrations of Ca, Mg, Zn, Cu, Na, Br, Mn, I and S than rural area residents. Concentrations of I and S from cancer patients, Mg, Zn, Al, Na, Mn and As from glassware workers were relatively higher. The results show that the trace element concentrations of the hair are possibly related to the trace element concentrations in the body.     

Trace element determination in beauty products by k0-instrumental neutron activation analysis

A recent study on trace elements in beauty products and cosmetics sold on the Asian market has shown the presence of high levels of U, Th and rare earth elements in so called “Hormesis cosmetics.” For the purpose of comparison, some more information about trace elements in European cosmetics would be useful. In this paper the results obtained using k ₀-standardised Instrumental Neutron Activation Analysis (k ₀-INAA) for more than 20 trace elements in 20 different beauty products collected from the European market are presented. We found traces of Ba, As and Sb which is in breach with European legislation. For some of the other elements like Cr and Co further speciation is needed in order to evaluate their presence in beauty products.     

Substoichiometric and non-destructive determination of trace impurities in high-purity optical glasses by neutron activation analysis

A method of radioactivation analysis has been developed for the determination of 17 elements as impurities in high-purity optical glasses. The substoichiometric extraction of platinum with dithizone was studied and a simple procedure was proposed for the determination of platinum. Copper and manganese were also determined substoichiometrically by the extractions with dithizone and with thenoyltrifluoracetone, respectively. The non-destructive γ-ray spectrometry using a Ge(Li) detector has been applied for the determination of the other 14 elements (Ag, Co, Cr, Eu, Fe, Ir, Sc, Zn, Cs, Hf, Rb, Sb, Ta and Tb). Impurity elements at the ppb level were analysed by the proposed method and it is shown that the method is reliable for the determination of trace impurities in high-purity optical glasses.     

Trace element determination in a mussel reference material using short irradiation instrumental neutron activation analysis

The production of certified reference materials in Brazil, and the consequent availability to national end users, is an important task for the enhancement of Metrology in Chemistry status in the country, as these materials are used for method validation, equipment calibration and for establishing metrological traceability links. In this study, Instrumental Neutron Activation Analysis (INAA) was applied to the determination of bromine, chlorine, magnesium, manganese, potassium and vanadium in a mussel reference material produced at IPEN-CNEN/SP. For the determination of these elements via the comparative INAA method, the respective analytical radionuclides, ⁸⁰Br, ³⁸Cl, ²⁷Mg, ⁵⁶Mn, ⁴²K and ⁵²V, are short lived and then, short irradiations are used. Six subsamples from two bottles of the Perna perna mussel reference material were analyzed. Each subsample was simultaneously irradiated with elemental standards for 10 s at the IEA-R1 research nuclear reactor through a pneumatic transfer system. After suitable decay periods, gamma radioactivity measurements were carried out, using a hyperpure germanium detector. The accuracy of the method was checked by using the NIST SRM 1566b–“Oyster Tissue” certified reference material. The comparison of the results obtained in this study to the robust mean of the interlaboratorial collaborative trial used for the characterization of the mussel reference material was performed via z-score tests. The comparison showed that the short irradiation INAA method is suitable for the characterization of new reference materials.     

Determination of impurities in high-purity solvents by neutron activation analysis

The determination of impurities in high-purity solvents, (acetone, isopropanol, trichloroethylene and trichlorotrifluoroethane) used in the production of integrated circuits was carried out by reactor neutron activation analysis. A special vacuum evaporation technique was used for the preconcentration of the solvents. The results showed that sodium and iron are the main impurity components in the solvents and on the other hand the quality of the solvents satisfies the specifications required by high-technology standards. The suspended solid particles in solvents were counted by a Microscopic Image Analysis System (MIAS).     

The simultaneous determination of silver,gold and mercury in high-purity lead by neutron activation analysis

A radiochemical method was developed to separate the group of the noble metals simultaneously from a lead matrix after irradiation with thermal neutrons. The resulting complex γ-spectrum was resolved by matrix calculus. Smoothing of the obtained data to determine the presence of small photopeaks among the background fluctuations, was done by convolution, based on a least squares approximation. The interference of antimony and bromine was studied. Amounts as low as 20–30 p.p.b. of Hg and less than 1 p.p.b. of Au were determined in the presence of up to 9 p.p.m. of Ag.     

Trace element determinations in shale oil products by neutron activation

Neutron activation offers some important advantages for the determination of selected trace elements in shale oil products. This paper gives techniques and results of a study of crude shale oil and naphtha, heavy distillate, and wax products of shale oil. The elements determined were Al, As, Au, Br, Ce, Cl, Co, Cr, Fe, Hg, I, K, Mn. Mo, Na, S, Sb, Se, V, and Zn. Some elements (Mn, Na, As) tend to accumulate in heavier fractions, whereas chlorine and iodine are concentrated in the more volatile fractions. The volatility of sulphur compounds in the shale oil products appears to be essentially uniform, with some tendency toward accumulation in distillation residues. The tendency for the trace elements to accumulate in the waxes that precipitated from cooled heavy distillates was very low.